ES2240482T3 - OXIDATION DYES. - Google Patents

Abstract

The invention relates to the paraaminophenol derivatives of formula (I), wherein R<1>, R<2>, R<3> and R<5> independently represent hydrogen, a C1-C4 alkyl group, a C2-C4 hydroxyalkyl group, R<2> and R<3> further represent fluoro, chloro, bromo, a C1-C4 alkoxy group or a hydroxy C2-C4 alkoxy group, R<5> may also represent an acyl group having 1-8 C atoms or a group of formula (II), and R<4> represents a hydrogen atom, an alkyl group, a C2-C4 hydroxyalkyl group, fluoro, chloro, bromo or a C1-C4 alkoxy group, and to their water-soluble salts, which are suitable as a developer component for producing an oxidative coloration. The preferred compounds are binuclear compounds, wherein R<5> represents a group of formula (II). The inventive oxidation colorants for keratin fibers, especially hair, contain the compounds of formula (I) preferably combined with further developers and/or coupling components and optionally combined with direct dyes.

Description

Oxidation dyes

The invention relates to the use of 2-hydroxy-5-aminobenzyl-piperazines and its water soluble salts as development components for the production of oxidation dyes and dyes for hair produced with them.

For dyeing keratin fibers, especially hair, the so-called oxidation dyes play a role special due to its intense colors and its properties of solidity, which are achieved at a relatively dye temperature Low and in short dye times. Such dyes contain a base of oxidation, in a suitable support, usually aqueous, which it is also called a development component and that constitutes a dye under the influence of air oxygen or oxidants by oxidative polymerization. By coupling with others development compounds or with the so-called compounds of coupling, which by themselves cannot constitute any dye, this dye can be intensified and its hue.

Good primary products of dyes oxidation must first meet the following requirements: they should develop the desired color nuances with sufficient intensity and solidity during oxidative coupling. In addition, they must have a good absorption capacity over the fibers, so that there should be no appreciable difference between fatigued and new hair that has subsequently grown (ability to match), especially in human hair. They must be resistant to light, heat, friction and influence of chemical reducing agents, for example, lotions for permanent ripple Finally, they should not dye the leather too much scalp, in case they are used as hair dye, and especially they must be harmless from the toxicological point of view and dermatological. In addition, the dye achieved must be able to be removed easily from hair by fading, in case you don't corresponds to the individual wishes of the person in particular and should be undone.

As development components are used normally primary aromatic amines with another amino group or free or substituted hydroxyl, which is in position for u ortho, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives, as well as 2,4,5,6-tetraaminopyrimidine and its derivatives.

Special representatives are, for example, p-phenylenediamine, p-toluylenediamine,  2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine,  2- (2 ', 5'-diaminophenyl) -ethanol, 2- (2 ', 5'-diaminophenoxy) -ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazol-5-one, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 2,4,5,6-tetraaminopyrimidine.

As coupling components are used generally m-phenylenediamine derivatives, naphthols, resorcinol and derivatives of resorcinol, pyrazolones and m-aminophenols As coupling substances are 1-naphthol, 1,5-, 2,7- and especially suitable 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, 2,4-dichloro-3-aminophenol, resorcinol, monomethyl ether of resorcinol, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-methylresorcinol, 5-methylresorcinol, m-phenylenediamine, 1-phenyl-3-methyl-pyrazol-5-one, 2,4-diaminophenoxyethanol, 1,3-bis- (2 ', 4'-diaminophenoxy) -propane, 2-amino-3-hydroxypyridine Y 2-Chloro-6-methyl-3-aminophenol.

Only with a development component or a special combination of coupling / development agent, normally it is not possible to maintain shades of color that seem natural on the hair. Therefore, in practice they are used normally combinations of different development components and coupling components Therefore, there is constantly the need for new improved dye primary products.

From WO 87/03475 A1, met the 4-amino-2-aminomethylphenols as development agents for the production of oxidation dyes For the hair. But the compounds disclosed there are not they still allow all the desired shades of color. Neither they still have satisfactory solid properties.

Therefore, the objective of the present invention was to find new development components that meet notably the requirements that products must meet primary oxidation dyes.

It has now been found that certain derivatives of para-aminophenol, to date not known, they largely meet the requirements that must be met by development components Thus, with the use of these components of development are obtained, with most of the components of known coupling, bright shades of color, which are extraordinarily solid in light and washing.

Object of the invention is the use of derivatives of para-aminophenol of formula I,

one

in which R 1, R 2, R 3 and R 5, independently of each other, represent hydrogen, a C 1 -C 4 alkyl group, a group C 2 -C 4 hydroxyalkyl, R 2 and R 3 they also represent fluorine, chlorine, bromine, an alkoxy group C 1 -C 4 or a hydroxyalkoxy group C 2 -C 4, R 5 is also an acyl moiety with 1-8 C atoms or a group of formula II,

2

and R 4 represents a represents a hydrogen atom, an alkyl group, a hydroxyalkyl group C 2 -C 4, fluorine, chlorine, bromine and a group alkoxy C_ {1} -C_ {{}},

and its water soluble salts as a component of development for the production of oxidation colorations.

Another special advantage of the compounds of development according to the invention, especially piperazines symmetrically substituted, in which R 5 is a group of Formula II, is its easy availability. Thus, it can be obtained by example the N, N'-bis- (2-hydroxy-5-aminobenzyl) -piperazine by reaction of piperazine with formaldehyde and 4-acetamidophenol and dissociation of acetyl groups of the N, N'-bis- (2-hydroxy-5-acetamidobenzyl) -piperazine formed this way. The derivatives of two-core para-aminophenol available from this way they represent developmental compounds especially preferred.

In a preferred embodiment of the invention, R 5 therefore represents a group of formula II. In this preferred embodiment is especially preferred choose the substituents R 5 according to formula II, so that the substituents 2-hydroxy-5-aminobenzyl attached to the piperazinyl bridges are the same.

In another preferred embodiment, the R 4 substituents and at least one of the R 2 substituents or R 3 are hydrogen.

In an embodiment especially preferred, the compound according to formula I is N, N'-bis- (2-hydroxy-5-aminobenzyl) -piperazine 4HCl.

Examples of alkyl moieties C 1 -C 4 mentioned as substituents in the framework of this application are methyl, ethyl, propyl groups, isopropyl and butyl. Preferred alkyl moieties are ethyl and methyl. Examples of C 2 -C 4 alkenyl moieties Preferred are vinyl and allyl. The alkoxy residues Preferred C 1 -C 4 according to the invention are, for example, a methoxy or ethoxy group. In addition, as examples preferred from a monohydroxyalkyl group C_ {1} -C_ {4} a group can be named hydroxymethyl, one 2-hydroxyethyl, one 3-hydroxypropyl or one 4-hydroxybutyl. A group is especially preferred 2-hydroxyethyl. An example of a group C2-C4 polyhydroxyalkyl preferred is the α, β-dihydroxyethyl group. Examples of a preferred C2-C4 hydroxyalkyl group are the examples mentioned under the group terms C 1 -C 4 monohydroxyalkyl and group C 2 -C 4 polyhydroxyalkyl, with the condition from which hydroxymethyl is excluded. Examples of halogen atoms they are atoms of F, Cl or Br, with atoms being especially preferred of Cl. The other terms used derive, according to the invention, from the definitions provided in this document. The Definitions agreed in this paragraph are also valid for formulas (E1), (E2), (E3), (E4) and (IIIa), as well as for (IIIb).

Para-aminophenol derivatives of formula I produce solid colorations in light and washing, especially by coupling with other components of development or with typical coupling compounds ("color modifier ", color modifier).

With coupling agents that carry a group phenolic hydroxyl, for example, intense colorations are obtained in the red and brown interval. Such primary products of oxidation dyes are used, on the one hand, for coloring of keratin fibers, on the other hand, in color photography. Be he especially prefers the use for fiber coloring of Keratin, especially human hair.

Another object of the invention are dyes of oxidation for keratin fibers, especially for hair, which contain in an aqueous support at least one derivative of para-aminophenol of formula I, as well as at least one other development compound and / or coupling. In this case, for Keratin fibers should be understood wool, feathers and skins, but especially human hair.

For the production of oxidation dyes according to the invention, the primary products of the oxidation dyes in a suitable aqueous support. Such supports are, for example, thick aqueous solutions, creams (emulsions), gels or foamy preparations containing surfactants, for example, shampoos or foam sprays or other Preparations that are suitable for application on hair. To produce shades preferably contain other compounds of development and / or coupling.

According to the invention, the components of Preferred coupling are

- m-aminophenol and its derivatives for example, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) -amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol Y 2,4-dichloro-3-aminophenol,

- o-aminophenol and its derivatives,

- m-diaminobenzene and its derivatives such as 2,4-diaminophenoxyethanol, 1,3-bis- (2 ', 4'-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) -benzene, 1,3-bis- (2 ', 4'-diaminophenyl) propane, 2,6-bis- (2'-hydroxyethylamino) -1-methylbenzene Y 1-amino-3-bis- (2'-hydroxyethyl) -aminobenzene,

- o-diaminobenzene and its derivatives such as acid 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,

- di or trihydroxybenzene derivatives as per example, resorcinol, monomethyl ether of resorcinol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,

- pyridine derivatives such as, 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine Y 3,5-diamino-2,6-dimethoxypyridine,

- naphthalene derivatives such as, 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,

- morpholine derivatives such as, 6-hydroxybenzomorpholine and 6-amino-benzomorpholine,

- quinoxaline derivatives such as, 6-methyl-1,2,3,4-tetrahydroquinoxaline,

- pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,

- indole derivatives such as, 4-hydroxy-indole, 6-hydroxy-indole and 7-hydroxy-indole,

- pyrimidine derivatives such as, 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine Y 4,6-dihydroxy-2-methylpyrimidine, or

- methylenedioxybenzene derivatives as per example, 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene Y 1- (2'-hydroxyethyl) -amino-3,4-methylenedioxybenzene.

As coupling compounds that are suitable for the modification of the colorations they are preferably used m-phenylenediamine derivatives, resorcinols, pyrazolones, m-aminophenols, aminohydroxypyridines mentioned at the beginning and others. To get more nuances intense in the red and brown range is especially preferred contain as coupling agent at least one m-aminophenol, a naphthol, a resorcinol or a derivative of these compounds.

As coupling substances are used of especially preferred way according to the invention 1-naphthol, 1,5, 2,7 and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-Chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxy-3,4-dimethylpyridine.

According to the invention it may be preferable to use as another development component a derivative of p-phenylenediamine or one of its physiologically salts compatible. Especially preferred are derivatives of p-phenylenediamine of formula (E1)

3

in the that

- G 1 represents a hydrogen atom, a C 1 -C 4 alkyl moiety, a moiety C 1 -C 4 monohydroxyalkyl, a moiety C 2 -C 4 polyhydroxyalkyl, a moiety (C 1 -C 4) alkoxy-(C 1 -C 4) alkyl, a 4'-aminophenyl moiety or an alkyl moiety C_ {1} -C_ {4}, which is substituted with a group containing nitrogen, with a phenyl moiety or 4'-aminophenyl,

- G 2 represents a hydrogen atom, a C 1 -C 4 alkyl moiety, a moiety C 1 -C 4 monohydroxyalkyl, a moiety C 2 -C 4 polyhydroxyalkyl, a moiety alkoxy- (C 1 -C 4) -alkyl- (C 1 -C 4), a C 1 -C 4 alkyl moiety, which is substituted with a group containing nitrogen

- G3 represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C 1 -C 4 alkyl moiety, a moiety C 1 -C 4 monohydroxyalkyl, a moiety C 2 -C 4 polyhydroxyalkyl, a moiety C 1 -C 4 hydroxyalkoxy, a C 1 -C 4 acetylaminoalkoxy, a moiety C 1 -C 4 mesylaminoalkoxy or a residue C 1 -C 4 carbamoylaminoalkoxy,

- G 4 represents a hydrogen atom, a halogen atom or a C 1 -C 4 alkyl moiety or

- when G 3 and G 4 are together in ortho position, they can form a group in common α, ome-alkylenedioxo that forms a bridge, such as an ethylenedioxy group.

Examples of nitrogen-containing groups of formula (E1) are especially amino groups, mono- groups.
alkyl- (C 1 -C 4) -amino, dialkyl- (C 1 -C 4) -amino, trialkyl- (C 1 -C 4) -ammonium groups, monohydroxyalkyl- (C 1 -C 4) -amino, imidazolinium and ammonium groups.

The p-phenylenediamines of the formula (E1) especially preferred are selected from p-phenylenediamine, p-toluylenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis - (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis - (β-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis - (β-hydroxyethyl) amino-2-chloroaniline, 2 - (β-hydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N - (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N - (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2 - (β-hydroxyethyloxy) -p-phenylenediamine, 2 - (β-acetylaminoethyloxy) -p-phenylenediamine, N - (β-methoxyethyl) -p-phenylenediamine Y 5,8-diaminobenzo-1,4-dioxane, as well as its physiologically compatible salts.

P-phenylenediamine derivatives of Very especially preferred formula (E1) according to the invention are p-phenylenediamine, p-toluylenediamine, 2 - (β-hydroxyethyl) -p-phenylenediamine Y N, N-bis - (β-hydroxyethyl) -p-phenylenediamine.

Furthermore, according to the invention it may be preferable. use compounds that contain the minus two aromatic nuclei that are substituted with amino groups and / or hydroxyl.

Among the two development components cores that can be used in dye compositions according to the invention, especially the compounds that can be named correspond to the following formula (E2), as well as its salts Physiologically compatible:

4

in the that:

- Z 1 and Z 2 represent, independently of each other, a hydroxyl moiety or NH2, which is optionally substituted by an alkyl moiety C 1 -C 4, for a monohydroxyalkyl moiety C_ {1} -C_ {4} and / or by a bridge Y or is optionally the part of a cyclic system that forms a bridge,

- the Y bridge represents an alkylene group with from 1 to 14 carbon atoms, such as a chain of linear or branched alkylene or an alkylene ring, which can be interrupted or terminated by one or more groups that contain nitrogen and / or one or more heteroatoms as oxygen atoms, sulfur or nitrogen and may eventually be substituted by one or several hydroxyl or C 1 -C 8 alkoxy moieties, or a direct link.

- G 5 and G 6 represent, independently of each other, a hydrogen or halogen atom, a C 1 -C 4 alkyl moiety, a moiety C 1 -C 4 monohydroxyalkyl, a moiety C 2 -C 4 polyhydroxyalkyl, a moiety C 1 -C 4 aminoalkyl or a direct link to the bridge Y,

- G 7, G 8, G 9, G 10, G 11 and G12 independently represent, among themselves, an atom of hydrogen, a direct link to the Y bridge or an alkyl moiety C_ {1} -C_ {4}, with the proviso that

- the compounds of formula (E2) only contain a bridge Y per molecule and

- the compounds of formula (E2) contain less an amino group, which carries at least one hydrogen atom.

The substituents used in the formula (E2) are defined according to the invention analogously to the embodiments previous.

The preferred two-core development components of formula (E2) are especially: N, N'-bis - (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino- propan-2-ol, N, N'-bis - (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -ethylene-
diamine, N, N'-bis- (4-aminophenyl) -tetra-methylenediamine, N, N'-bis - (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -tetramethylenediamine, N , N'-bis- (4-methyl-aminophenyl) -tetramethylenediamine, N, N'-bis- (ethyl) -N, N'-bis- (4'-aminophenyl-3'-methylphenyl) -ethylenediamine, bis- (2-hydroxy-5-aminophenyl) -methane, 1,4-bis- (4'-aminophenyl) -diazacycloheptane, N, N'-bis- (2-hydroxy-5-aminobenzyl) -piperazine, N- (4 '-aminophenyl) -p-phenylenediamine and 1,10-bis- (2', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and its physiologically compatible salts.

Two core development components of very especially preferred formula (E2) are N, N'-bis - (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, bis- (2-hydroxy-5-aminophenyl) -methane, N, N'-bis- (4'-aminophenyl) -1,4-diazacycloheptane Y 1,10-bis- (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane or one of its physiologically compatible salts.

Furthermore, according to the invention it may be preferable. use as a development component a derivative of p-aminophenol or one of its salts physiologically compatible. Especially preferred are derivatives of p-aminophenol of formula (E3)

5

in the that

- G13 represents a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl moiety, a C 1 -C 4 monohydroxyalkyl moiety, a C2-C4 polyhydroxyalkyl moiety, a moiety (C 1 -C 4) alkoxy-(C 1 -C 4) alkyl, an aminoalkyl (C 1 -C 4) moiety, a moiety hydroxyalkyl (C 1 -C 4) -amino, a C 1 -C 4 hydroxyalkoxyl moiety, a moiety hydroxyalkyl- (C 1 -C 4) -aminoalkyl (from C_ {1} to C_ {4}) or a remainder dialkyl- (C 1 -C 4) - amino-alkyl (C_ {1} -C_ {{}}) and

- G 14 represents a hydrogen atom or of halogen, a C 1 -C 4 alkyl moiety, a moiety C 1 -C 4 hydroxyalkyl, a moiety C 2 -C 4 polyhydroxyalkyl, a moiety alkoxy- (C 1 -C 4) -alkyl- (C 1 -C 4), a C 1 -C 4 aminoalkyl moiety or a moiety C 1 -C 4 cyanoalkyl,

- G 15 represents hydrogen, an alkyl moiety C 1 -C 4, a hydroxyalkyl moiety C 1 -C 4, a polyhydroxyalkyl moiety C 2 -C 4, a phenyl moiety or a benzyl moiety, Y

- G 16 represents hydrogen or an atom of halogen

The substituents used in the formula (E3) are defined according to the invention analogously to the embodiments previous.

The p-aminophenols of the formula (E3) preferred are especially p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxy-methylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (2-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2 - (β-hydroxyethyl-aminomethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 2,6-dichloro-4-aminophenol, 4-amino-2 - ((diethylamino) methyl) phenol, as well as its physiologically compatible salts.

Compounds of formula (E3) very especially Preferred are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol Y 4-amino-2 - ((diethylamino) methyl) phenol.

In addition, the development component can selected from o-aminophenol and its derivatives, such as 2-amino-4-methylphenol or 2-amino-4-chlorophenol.

In addition, the development component can selected from heterocyclic development components, such as derivatives of pyridine, pyrimidine, pyrazole, pyrazol-pyrimidine and its salts physiologically compatible. According to the invention, pyrimidine or derivatives are preferred. of pyrazole

Preferred pyrimidine derivatives are especially the compounds described in the German patent DE 2 359 399, publication for request information of Japanese patent JP 02019576 A2 or in the publication for information of patent application WO 96/15765, as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

Preferred pyrazole derivatives are especially the compounds described in DE 3 patents 843 892, DE 4 133 957 and in patent applications WO 94/08969, WO 94/08970, EP-740931 and DE 195 43 988, as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1 - (β-hydroxyethyl) -pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) -pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1 - (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) -pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole Y 3,5-diamino-4 - (β-hydroxyethyl) amino-1-methylpyrazole.

Preferred pyridine derivatives are especially the compounds described in GB 1 patents 026 978 and GB 1 153 196, as 2,5-diamino-pyridine, 2- (4-methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2 - (β-methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

The derivatives of Preferred pyrazol-pyrimidine are especially those derivatives of pyrazol- [1,5-a] -pyrimidine from the following formula (E4) and its tautomeric forms, as long as there is a tautomeric equilibrium:

6

in the that:

- G 17, G 18, G 19 and G 20 independently represent each other, a hydrogen atom, a C 1 -C 4 alkyl moiety, an aryl moiety, a C 1 -C 4 hydroxyalkyl moiety, a moiety C 2 -C 4 polyhydroxyalkyl, a moiety alkoxy- (C 1 -C 4) -alkyl- (C 1 -C 4), a C 1 -C 4 aminoalkyl moiety, which optionally it can be protected by a rest acetyl ureido or sulfonyl, a moiety alkyl- (C 1 -C 4) -amino-alkyl (C_ {1} -C_ {4}), a remainder di- [alkyl- (C 1 -C 4)] - aminoalkyl (C 1 -C 4), so that the dialkyl moieties they can optionally form a carbon cycle or a heterocycle with 5 or 6 chain links, a hydroxyalkyl moiety C_ {1} -C_ {or} dihydroxyalkyl- (C 1 -C 4) -aminoalkyl (C 1 {C 4}),

- the X remains represent, independently each other, a hydrogen atom, an alkyl moiety C_ {1} -C_ {4}, an aryl moiety, a moiety C 1 -C 4 hydroxyalkyl, a moiety C 2 -C 4 polyhydroxyalkyl, a moiety C 1 -C 4 aminoalkyl, a moiety alkyl- (C 1 -C 4) -amino-alkyl (C_ {1} -C_ {4}), a remainder di [alkyl- (C 1 -C 4)] - aminoalkyl (C 1 -C 4), so that the dialkyl moieties they can optionally form a carbon cycle or a heterocycle with 5 or 6 chain links, a hydroxyalkyl moiety C_ {1} -C_ {or} dihydroxyalkyl- (C 1 -C 4) -aminoalkyl (C 1 -C 4), an amino moiety, an alkyl moiety C_ {1} -C_ {or} di-hydroxyalkyl- (C 1 -C 4) -amino, a halogen atom, a carboxylic acid group or a group of sulfonic acid,

- i has the value of 0, 1, 2, or 3,

- p has the value of 0 or 1,

- q has the value of 0 or 1 and

- n has the value of 0 or 1

with the condition of

- the sum of p + q is different from 0,

- when p + q is equal to 2, n has the value of 0, and the groups NG 17 G 18 and NG 19 G 20 occupy the positions (2,3); (5.6); (6.7); (3.5) or (3.7);

- when p + q is equal to 1, n has the value of 1, and the groups NG 17 G 18 (or NG 19 G 20) and the group OH occupy the positions (2,3); (5.6); (6.7); (3.5) or (3.7);

The substituents used in the formula (E4) are defined according to the invention analogously to the embodiments previous.

When the pyrazol- [1,5-a] -pyrimidine from the formula (E4) above contains a hydroxyl group in one of the positions 2, 5 or 7 of the ring system, there is a balance tautomeric, which is represented for example in the following scheme:

7

Between the pyrazole- [1,5-a] -pyrimidines of the formula (E4) above can be specially named:

- pyrazol- [1,5-a] -pyrimidin-3,7-diamine;

- 2,5-dimethylpyrazol- [1,5-a] -pyrimidin-3,7-diamine;

- pyrazol- [1,5-a] -pyrimidin-3,5-diamine;

- 2,7-dimethylpyrazol- [1,5-a] -pyrimidin-3,5-diamine;

- 3-aminopyrazole- [1,5-a] -pyrimidin-7-ol;

- 3-aminopyrazole- [1,5-a] -pyrimidin-5-ol;

- 2- (3-aminopyrazole- [1,5-a] -pyrimidin-7-ylamino) -ethanol;

- 2- (7-aminopyrazole- [1,5-a] -pyrimidin-3-ylamino) -ethanol;

- 2 - [(3-aminopyrazole- [1,5-a] -pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol;

- 2 - [(7-aminopyrazole- [1,5-a] -pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol;

- 5,6-dimethylpyrazol- [1,5-a] -pyrimidin-3,7-diamine;

- 2,6-dimethylpyrazol- [1,5-a] -pyrimidin-3,7-diamine;

- 2,5, N7, N7-tetramethylpyrazol- [1,5-a] -pyrimidin-3,7-diamine;

as well as its physiologically compatible salts and its tautomeric forms, when there is a balance Tautomeric

The pyrazole- [1,5-a] -pyrimidines of the formula (E4) above can be produced by cycling starting of an aminopyrazole or hydrazine, as described in the bibliography.

According to the invention, very development components especially preferred are selected from p-phenylenediamine, p-toluylenediamine, p-aminophenol, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, N, N-bis- (2'-hydroxyethyl) -p-phenylenediamine, 4-amino-3-methylphenol, 4-amino-2 - ((diethylamino) -methyl) -phenol, 2-aminomethyl-4-aminophenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine Y 4,5-diamino-1- (2'-hydroxyethyl) -pyrazole.

Hair dyes according to the invention they contain both the development components as well as the coupling components preferably in an amount of from 0.005 to 20% by weight, preferably 0.1 to 5% in weight, in each case with respect to the total oxidation dye. In this sense, the development components and the components of coupling are generally used in approximately quantities equimolar to each other. When equimolar use has also shown be appropriate, then a certain excess of the primary products of the individual oxidation dyes, so that the development components and the components of coupling can be contained in a molar ratio of from 1: 0.5 to 1: 2.

A hair color that looks natural comes from a coloring process when applied to the hair dye they also use indole or indoline derivatives as products Primary dyes analogous to natural.

Therefore, in another embodiment, additionally use indoles and / or indolines, which at least have a hydroxyl or amino group, preferably as a substituent in a hexagonal ring. These groups can carry other substituents, for example, in the form of an etherification or esterification of the hydroxyl group or an alkylation of the group Not me.

They are especially very suitable as precursors from hair dyes analogous to natural ones 5,6-dihydroxyindoline derivatives of formula (IIIa),

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8

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in which, independently between yes,

R1 represents hydrogen, an alkyl group C 1 -C 4, a cycloalkyl group C 3 -C 6, an alkenyl group C 2 -C 4 or a hydroxyalkyl group C_ {1} -C_ {{}},

R2 represents hydrogen or a -COOH group, of so that the -COOH group can also be presented as salt with a physiologically compatible cation,

R 3 represents hydrogen or an alkyl group C_ {1} -C_ {{}},

R 4 represents hydrogen, an alkyl group C_ {1} -C_ {4} or a group -CO-R 6, so that R 6 represents a group C 1 -C 4 alkyl, and

R 5 represents one of the groups named in R 4,

as well as physiologically compatible salts of these compounds with an organic or inorganic acid.

Especially preferred indoline derivatives they are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxy indoline, acid 5,6-dihydroxyindoline-2-carboxylic acid, as well as 6-hydroxyindoline, 6-aminoindoline and the 4-aminoindoline.

Within this group should stand out especially N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-Butyl-5,6-Dihydroxyindoline and especially 5,6-dihydroxyindoline.

In addition, they are remarkably suitable as precursors of hair dyes analogous to natural 5,6-dihydroxyindole derivatives of formula (IIIb),

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9

in which, independently between yes,

R1 represents hydrogen, an alkyl group C 1 -C 4, a cycloalkyl group C 3 -C 6, an alkenyl group C 2 -C 4 or a hydroxyalkyl group C_ {1} -C_ {{}},

R2 represents hydrogen or a -COOH group, of so that the -COOH group can also be presented as salt with a physiologically compatible cation,

R 3 represents hydrogen or an alkyl group C_ {1} -C_ {{}},

R 4 represents hydrogen, an alkyl group C_ {1} -C_ {4} or a group -CO-R 6, so that R 6 represents a group C 1 -C 4 alkyl, and

R 5 represents one of the groups named in R 4,

as well as physiologically compatible salts of these compounds with an organic or inorganic acid.

Especially preferred indole derivatives are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxy-indole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, acid 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.

Within this group should stand out especially N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, as well as especially 5,6-dihydroxyindole.

Indoline and indole derivatives can used in dyes according to the invention as well as free bases as well as in the form of its physiologically compatible salts with inorganic or organic acids, for example, hydrochlorides, sulfates and hydrobromides. Indoline and indole derivatives are contained in these normally in amounts of 0.05-10% in weight, preferably 0.2-5% by weight.

In addition, explicit reference is made regarding to the dyes that can be used for dyes and agents hair color in monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; Dyes direct), as well as in chapter 8, pages 264-267; Primary products of the dyes of oxidation), published as volume 7 of the "Dermatology" series (editors: Ch. Culnan and H. Maibach), publisher Marcel Dekker Inc., New York, Basel, 1986, as well as "Europäische Invent der Kosmetik-Rohstoffe "(European Inventory of cosmetic raw materials), edited by the European Union, available as a floppy disk in Bundesverband Deutscher Industrie- und Handelsunternehmen für Arzneimittel, Reformwaren und Körperpflegemittel e.V., (Federal Association of Industry and Companies marketers of medicines, natural products and products of body care), Mannheim.

As support components are used preferably

- wetting and emulsifying agents

- thickening agents

- reducing agents (antioxidants)

- hair care additives

- aromas and

- solvents such as water, glycols or lower alcohols

As wetting and emulsifying agents are suitable, for example, anionic, zwitterionic surfactants, ampholytic and non-ionic. Surfactants can also be used cationic to achieve certain effects. But in many cases it has proved advantageous to select surfactants from of anionic, zwitterionic or non-ionic surfactants.

In the preparations according to the invention are suitable as anionic surfactants, all substances Superficially active anionic suitable for use in the body. These are characterized by an anionic group that it makes water soluble, such as, for example, carboxylate group, sulfate, sulphonate or phosphate and a lipophilic alkyl group with approximately from 10 to 22 C atoms. Additionally they can also be contained in the molecule glycol or polyglycol ether groups, groups ester, ether and amido, as well as hydroxyl groups. Examples of suitable anionic surfactants are, respectively, in the form of sodium, calcium and ammonium salts, as well as mono, di and trialcanolamonium with 2 or 3 C atoms in the alkanol group,

-

acids linear fats with 10 to 22 C atoms (soaps),

-

acids ether carboxylic formula R-O- (CH 2 -CH 2 O) x -CH 2 -COOH, wherein R is a linear alkyl group with 10 to 22 atoms of C and x = 0 or 1 to 16,

-

acylsarcosides with 10 to 18 atoms of C in the acyl group,

-

aciltaurates with 10 to 18 C atoms in the acyl group,

-

acylisethionates with 10 to 18 atoms of C in the acyl group,

-

ester mono and dialkyl sulfosuccinic acid with 8 to 18 C atoms in the alkyl and monoalkyl polyoxyethyl ester group of acid sulfosuccinic with 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups,

-

linear alkanesulfonates with 12 to 18 C atoms,

-

sulfonates of linear alpha-olefin with 12 to 18 atoms of C,

-

ester alpha-sulfo-fatty acid methyl acid with 12 to 18 atoms of C,

-

alkyl sulfates and alkyl sulfates formula polyglycol ether R-O (CH 2 -CH 2 O) x -SO 3 H, wherein it is preferably a linear alkyl group with from 10 to 18 atoms of C and x = 0 or 1 to 12,

-

mixtures of hydroxyl sulfonates superficially active, according to the document DE-A-37 25 030,

-

hydroxyalkyl polyethylene glycol ethers and / or hydroxyalkylene propylene glycol sulfated ethers, according to DE-A-37 23 354,

-

unsaturated fatty acid sulfonates with 12 to 24 C atoms and 1 to 6 double bonds, according to the document DE-A-39 26 344,

-

esters of tartaric acid and acid citric with alcohols, which represent addition products of approximately 2-15 ethylene oxide molecules and / or propylene oxide to fatty alcohols with from 8 to 22 atoms of C.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and acids ether carboxylic acids with 10 to 18 C atoms in the alkyl group and up to 12 groups of glycol ether in the molecule, as well as especially salts of carboxylic acids C 8 -C 22 saturated and especially unsaturated, such as oleic acid, stearic acid, isostearic acid and palmitic acid.

Non-ionogenic surfactants contain as hydrophilic groups, for example, a polyol group, a group polyalkylene glycol ether or a combination of polyol groups and polyglycol ether. Such compounds are, for example,

-

addition products from 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide at linear fatty alcohols with 8 to 22 C atoms, to fatty acids with from 12 to 22 atoms of C and to alkylphenols with from 8 to 15 atoms of C in the alkyl group,

-

monkey and diesters of C 12 -C 22 fatty acids of addition products of from 1 to 30 moles of ethylene oxide to glycerin,

-

rent C_ {8} -C_ {22} -mono and oligoglycosides and their ethoxylated analogs, as well as

-

addition products from 5 to 60 moles of ethylene oxide to castor oil and castor oil hard.

Preferred non-ionic surfactants are alkyl polyglycosides of the general formula R'O- (Z) x. These Compounds are characterized by the following parameters.

The alkyl radical R 'contains from 6 to 22 atoms of carbon and can be both linear and branched. Preferably are linear and branched primary aliphatic residues with methyl in position 2. Such alkyl moieties are for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. By way of Especially preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. If so-called ones are used "oxo-alcohols" as starting materials Compounds with an odd number of carbon atoms predominate in the alkyl chain.

The alkyl polyglycosides that can be used according to the invention they can only contain, for example, a residue fixed R1 alkyl. But normally, these compounds are produced starting from natural fats and oils or mineral oils. In this In this case, R-alkyl mixtures are presented as mixtures corresponding to the starting compounds or so corresponding to the respective regeneration of these compounds.

Especially preferred are those alkyl polyglycosides, in which R 'consists of

- essentially C 8 alkyl groups and C 10,

- essentially C 12 alkyl groups and C_ {14},

- essentially alkyl groups C_ {8} -C_ {16},

- essentially alkyl groups C_ {12} -C_ {16}.

As a constituent element of sugar Z can any mono or oligosaccharide is used. Normally used sugars with 5 or 6 carbon atoms, as well as the corresponding ones oligosaccharides Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, alose, altrosa, Mannose, gummy, idosa, talosa and sucrose. The elements Preferred sugar constituents are glucose, fructose, galactose, arabinose and sucrose; it is especially preferred glucose.

The alkyl polyglycosides that can be used according to the invention they contain an average of 1.1 to 5 units of sugar. Alkyl polyglycosides with values of x of from 1.1 to 1.6. Especially preferred are alkyl glycosides in which x is 1.1 to 1.4.

In addition to their surfactant effect, the alkyl glycosides can also serve to improve the fixation of The aromatic components in the hair. The expert too preferably resort to this class of substances like others substances contained in the preparations according to the invention, in the if an effect of the essential oil is desired on the hair that overlaps the duration of hair treatment.

Also according to the invention can be used alkoxylated homologs of the named alkyl polyglycosides. These counterparts can contain on average up to 10 units of oxide ethylene and / or propylene oxide per alkyl glycoside unit.

In addition, they can also be used, especially as co-surfactants, zwitterionic surfactants. Zwitterionic surfactants are those compounds superficially active that carry at least one group in the molecule quaternary ammonium and at least one group -COO (-)} or -SO_ {3} (-)}. Zwitterionic surfactants especially suitable are the so-called betaines, such as glycinate N-alkyl-N, N-dimethylammonium, for example, coconut alkyldimethylammonium glycinate, glycinate N-acyl-aminopropyl-N, N-dimethylammonium, for example, coconut acylaminopropyldimethylammonium glycinate and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazoline with from 8 to 18 C atoms respectively in the alkyl group or acyl, as well as acylaminoethylhydroxyethylcarboxymethylglycinate coconut. A preferred zwitterionic surfactant is the derivative of fatty acid amide known as Cocamidopropyl Betaine (Cocamidopropyl betaine) according to the INCI designation.

Ampholytic surfactants are also especially suitable as co-surfactants. By ampholytic surfactants are understood as those compounds superficially active, which without counting an alkyl or acyl group C 8 -C 18 in the molecule contain at least a free amino group and at least one -COOH or -SO3H group and that They are suitable for forming internal salts. Examples of surfactants Suitable ampholytics are N-alkylglycins, acids N-alkylpropionic acids N-alkylaminobutyric acids, acids N-alkyliminodipropionics, N-hydroxyethyl-N-alkylamidopropylglycins, N-alkyltaurines, N-alkylsarcosines, acids 2-alkylaminopropionic acids alkylaminoacetics with for example 8 to 18 C atoms respectively in the alkyl group. Ampholytic Surfactants Especially preferred are the Coconut N-alkylaminopropionate, Coconut acylaminoethylaminopropionate and acylsarcosine C_ {12-18}.

As cationic surfactants they are used according to the invention especially those of the type of compounds of quaternary ammonium, esterquats and amidoamines.

Preferred quaternary ammonium compounds they are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkylmethylammonium chlorides, for example, cetyltrimethylammonium, stearyltrimethylammonium chloride, distearyl dimethyl ammonium, lauryl dimethyl ammonium chloride, lauryl dimethylbenzylammonium and tricethylmethylammonium chloride, as well as the imidazolium compounds known as Quaternium-27 and Quaternium-83 by INCI denominations. The long alkyl chains of surfactants mentioned above preferably have 10 to 18 carbon atoms.

In the case of esterquats it is about known compounds containing as structural element the less both an ester function and also at least one ammonium group quaternary. Preferred esterquats are ester salts quaternized fatty acids with triethanolamine, ester salts quaternized fatty acids with diethanolalkylamines and salts of quaternized fatty acid ester with 1,2-dihydroxypropyldialkylamines. Such products they are sold for example, under the trade names Stepantex®, Dehyquart® and Armocare®. Examples of such esterquats are the Armocare® VGH-70 products, a chloride of N, N-bis (2-palmitoyloxyethyl) dimethyl ammonium, as well as Dehyquart® F-75 and Dehyquart® AU-35

Alkylamidoamines are normally produced by amidation of natural or synthetic fatty acids and parts of fatty acids with dialkylaminoamines. The stearamidopropyl dimethylamine available in the trade with the designation Tegoamid® S 18 represents a compound especially suitable according to the invention of this group of substances

Quaternized protein hydrolysates represent other cationic surfactants that can be used according to the invention.

According to the invention, the cationic silicone oils such as products commercially available Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylammodimethicone), Dow emulsion Corning 929 (which contains a hydroxylamino modified silicone, which is also called amodimethicone), SM-2059 (Manufacturer: General Electric), SLM-55067 (manufacturer: Wacker), as well as Abil® - Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; dicuaternary polydimethylsiloxane, Quaternium-80).

The commercial product Glucquat® 100, according to the INCI nomenclature, a "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride "represents an example of a Quaternary sugar derivative that can be used as cationic surfactant.

In the case of compounds with alkyl groups used as surfactants can be substances homogeneous. However, it is usually preferred to start from materials native vegetable or animal raw materials for the production of these substances, so that mixtures of substances with different lengths of alkyl chains, depending on the respective raw material.

In the case of the surfactants they represent ethylene oxide and / or propylene oxide addition products to fatty alcohols or derivatives of these addition products, may be used both products with a distribution of counterparts "normal" as well as those with a distribution of close counterparts. In this sense, by distribution of counterparts "normal" means mixtures of homologs that are obtained by the reaction of fatty alcohol and alkylene oxide using metals alkalines, alkali metal hydroxides or metal alcoholates alkaline as catalysts. Peer Distributions narrow ones are obtained on the contrary when used as catalysts for example, hydrotalcite, metal salts alkaline earth of ether carboxylic acids, oxides, hydroxides or alkaline earth metal alcoholates. The use of products with a narrow counterpart distribution.

On the one hand they are suitable as thickening agents High molecular weight polysaccharide or polypeptide derivatives water soluble, for example, cellulose ether or starch, gelatin, vegetable gums, biopolymers (xanthan gum) or synthetic polymers water soluble such as polyvinylpyrrolidone, polyvinyl alcohol, poly (ethylene oxides), polyacrylamides, polyurethanes, polyacrylates and others. On the other hand, preparations containing surfactants can also thicken by solubilization or emulsion of polar lipids. Such lipids they are, for example, fatty alcohols with 12-18 atoms of C, fatty acids (free) with 12-18 C atoms, partial fatty acid glycerides, fatty acid esters of sorbitan, fatty acid alkanolamides, fatty acids or alcohols little oxyethylated fatty acids, lecithin, sterine. Finally also gel-shaped supports can also be generated based on gels aqueous soap, for example, ammonium oleate. Are used preferably thickening agents such as agar-agar, guar gum, alginate, xanthan gum, gum arabic, karaya gum, flour of carob seeds, flax seed gums, dextrans, cellulose derivatives, for example, methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as for example, bentonite or fully synthetic hydrocolloids such as for example, polyvinyl alcohol.

Reducing agents (antioxidants), which added to the support to prevent premature oxidative development of dye before application to hair, for example, sodium sulphite or sodium ascorbate.

Hair care additives can be, for example, greases, oils or waxes in emulsified form, additives which give structure such as glucose or pyridoxine, components that fan, for example, water soluble proteins, degradation products of proteins, amino acids, polymers water-soluble cationics, silicones, vitamins, such as Panthenol or plant extracts.

Finally, they may contain aromatic substances. and solvents such as glycols such as 1,2-propylene glycol, glycerin, glycol ether as per example, butyl glycol, ethyldiglycol or monovalent alcohols lower as ethanol or isopropanol.

Additionally they may still contain others adjuvants that facilitate the stability and properties of application of oxidation dyes, for example, formers of complexes such as EDTA, NTA or organophosphonates, swelling agents and penetration such as urea, guanidine, hydrogen carbonates, buffer salts such as, for example, chloride ammonium, ammonium citrate, ammonium sulfate or salts of alkanolammonium and optionally propellant gases.

In addition, the agents according to the invention can preferably still contain an active substance of conditioning, selected from the group consisting of surfactants cationic, cationic polymers, alkylamidoamines, oils paraffinics, vegetable oils and synthetic oils.

Preferably the cationic polymers can Be active conditioning substances. These are normally polymers containing a quaternary nitrogen atom, by example in the form of an ammonium group.

Preferred cationic polymers are by example

-

quaternized cellulose derivatives, commercially available under the names Celquat® and Polymer JR®. Preferred cellulose derivatives are the compounds Celquat® H 100, Celquat® L 200 and Polymer JR® 400.

-

you go out dimethyldiallylammonium polymers and their acid copolymers acrylic, as well as esters and amides of acrylic acid and acid methacrylic Examples of such cationic polymers are the commercially available products under the denominations Merquat® 100 (poly (dimethyldiallylammonium chloride)), Merquat® 550 (copolymer of chloride dimethyldiallylammonium acrylamide) and Merquat® 280 (dimethyldiallylammonium acid chloride copolymer acrylic).

-

vinyl pyrrolidone copolymer with quaternized derivatives of dialkylamino acrylate and methacrylate, such as copolymers of vinyl pyrrolidone dimethylaminomethacrylate quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat®734 and Gafquat®755.

-

copolymers of vinyl pyrrolidone-methimidazolinium chloride, such as They are offered under the name Luviquat®.

-

poly (vinyl alcohol) quaternized

as well as polymers with nitrogen atoms quaternary in the polymeric main chain known under the denominations

- Polyquaternium 2,

- Polyquaternium 17,

- Polyquaternium 18 and

- Polyquaternium 27.

Polymers are especially preferred. cationics of the first four groups named, very Especially preferred are Polyquaternium-2, Polyquaternium-10 and Polyquaternium-22.

In addition, as active substances of conditioning silicone oils are suitable, especially dialkyl and alkylarylsiloxanes, for example, dimethylpolysiloxane and methylphenylpolysiloxane, as well as their analogues alkoxylated and quaternized. Examples of such silicones are those products sold by Dow Corning under the designations DC 190, DC 200, DC 344, DC 345 and DC 1401, as well as commercial products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylammodimethicone), Dow Corning® 929 emulsion (which contains a hydroxylamino modified silicone, which also It is called amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (Manufacturer: Wacker), as well as Abil® - Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; quaternary polydimethylsiloxane, Quaternium-80).

Conditioning active substances that can also be used are paraffinic oils, alkenes synthetically produced oligomers, as well as vegetable oils such as jojoba oil, sunflower oil, orange oil, oil of almond, wheat germ oil and bone oil peach.

Likewise, conditioning compounds of Suitable hair are phospholipids, for example, soy lecithin, egg lecithin and cephalins.

Other active substances, adjuvants and additives are for example

-

nonionic polymers such as, vinyl pyrrolidone / vinyl acrylate copolymers, copolymers of polyvinylpyrrolidone and vinyl pyrrolidone / vinyl acetate and polysiloxanes,

-

zwitterionic and amphoteric polymers such as chloride copolymers of acrylamidopropyl-trimethylammonium / acrylate and Octyl acrylamide / methyl methacrylate / methacrylate copolymers tert-butylaminoethyl / methacrylate 2-hydroxypropyl,

-

anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, copolymers of vinyl acetate / crotonic acid, copolymers of vinyl pyrrolidone / vinyl acrylate, acetate copolymers vinyl / butyl maleate / isobornyl acrylate, copolymers of methyl vinyl ether / maleic acid anhydride and acid terpolymers acrylic / acrylate ethyl / N-tert-butyl acrylamide,

-

structuring agents such as maleic acid and lactic acid,

-

conditioning compounds hair such as phospholipids, for example, soy lecithin, lecithin of egg and cephalins,

-

protein hydrolysates, especially, elastin, collagen, keratin hydrolysates, of milk protein, soy protein and wheat protein, its condensation products with fatty acids, as well as quaternized protein hydrolysates,

-

essential oils, dimethylisosorbide and cyclodextrins,

-

solvents and auxiliary solvents such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol,

-

active substances that improve the fiber structure, especially mono, di and oligosaccharides such as glucose, galactose, fructose, fruit sugar and lactose,

-

amines quaternized as methyl-1-alkylamidoethyl-2-alkylimidazolinium-methosulfate

-

defoamers such as silicone,

-

dyes to dye the agent,

-

anti-dandruff active substances such as piroctone olamine, omadine zinc and climbazole,

-

light stabilizing agents, especially derivatized benzophenones, acid derivatives cinnamic and triazines,

-

substances to adjust the pH value, such as usual acids, especially acids groceries and bases,

-

active substances such as allantoin, pyrrolidoncarboxylic acids and their salts, as well as bisabolol,

-

vitamins, provitamins and precursors of vitamins, especially those in group A, B3, B5, B6, C, E, F and H,

-

plant extracts, such as extracts green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, flowers of linden, almond, aloe vera, pine needles, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, kivi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadow lunch, serpol, yarrow, thyme, melissa, gatuña, Tusilage, Marshmallow, Meristem, Ginseng and Root ginger,

-

cholesterol,

-

agents that give consistency as sugar esters, polyol esters or polyolalkyl ether,

-

fat and waxes such as spermaceti oil, beeswax, mountain wax and paraffins,

-

fatty acid alkanolamides,

-

complex trainers like EDTA, NTA, β-alanindiacetic acid and acids phosphonic,

-

swelling and penetration substances such as glycerin, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas as well as primary phosphates, secondary and tertiary,

-

opacifiers such as latex, copolymers of styrene / PVP and styrene / acrylamide

-

pearl luster agents like mono and ethylene glycol distearate, as well as distearate of PEG-3,

-

pigments,

-

peroxide stabilizers hydrogen and other oxidizing agents,

-

propellants as mixtures of propane-butane, N2O, dimethyl ether, CO2 and air,

-

antioxidants

In reference to other optional components as well as the quantities used of these components is remitted explicitly to the corresponding manuals known to the expert, for example, K. Schrader, Grundlagen und Rezepturen der Kosmetika, 2nd edition, Hüthig Buch editorial, Heidelberg, 1989.

In addition, certain can also be used direct dyes to achieve certain effects of coloration.

Preferably, hair dyes according to the invention contain, in addition to the primary products of oxidation dyes, additionally direct dyes usual to give another modification of the nuances of color. The direct dyes are preferably nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. The Preferred direct dyes are compounds known to the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9 and Acid Black 52, as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis - (β-hydroxyethyl) -amino-2-nitrobenzene, 3-nitro-4 - (β-hydroxyethyl) -aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) -amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, acid 4-amino-2-nitrodiphenylamin-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, pyramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, acid 4-ethylamino-3-nitrobenzoic Y 2-Chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

In addition, the agents according to the invention can contain a cationic direct dye. In this sense, it they especially prefer:

(to)

triphenylmethane dyes cationic, such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,

(b)

aromatic systems that are substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as

(C)

direct dyes containing a heterocycle, which at least has a nitrogen atom quaternary, as they are named for example in the document EP-A2-998 908, which is done explicit reference at this point, in claims 6 to eleven.

The preferred cationic direct dyes of group (c) are especially the following compounds:

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10

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eleven

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12

13

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14

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fifteen

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16

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17

18

The compounds of the formulas (DZ1), (DZ3) and (DZ5) are direct cationic dyes of group (c) very especially preferred. Direct cationic dyes, which are sold under the trademark Arianor®, are direct dyes Especially preferred cationics according to the invention.

In a special embodiment, the dyes for hair according to the invention contain direct dyes selected from the group of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols, such as compounds known by international denominations or trade names HC Yellow 2, HC Yellow 4, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Nitroblau, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16, acid pyramic and Rodol 9 R, in an amount from 0.01 to 20% by weight, with respect to oxidation dye for total hair. According to the invention, especially preferred direct dyes they are acid 4-amino-2-nitrodiphenylamin-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, Rodol 9 R and HC Red BN.

The agents according to the invention according to this form of embodiment contain direct dyes preferably in an amount of from 0.01 to 20% by weight, based on total dye

The oxidative development of the coloration can generally take place with oxygen from the air. However, preferably a chemical oxidizing agent is used, especially when, in addition to coloring, a lightening effect on human hair is desired. Oxidizing agents include persulfates, chlorites and especially hydrogen peroxide or its addition products to urea, melamine, as well as sodium borate. The oxidizing agent can also be applied to the hair together with a catalyst, which activates the oxidation of the primary products of the oxidation dyes, for example, by oxygen from the air. Such catalysts are, for example, transition metal compounds, iodides, quinones or certain enzymes. Suitable enzymes are, for example, peroxidases, which can clearly reinforce the effect of small amounts of hydrogen peroxide. In addition, such enzymes are suitable according to the invention since, with the aid of air oxygen, they oxidize directly the primary products of oxidation dyes, such as lacquers, or generate small amounts of hydrogen peroxide in situ and thus activate Biocatalytic mode the oxidation of the primary products of the dyes. Catalysts especially suitable for the oxidation of dye precursors are the so-called 2-electron oxidoreductases in combination with the substrates specific for them, for example

- pyranose oxidase and for example, D-glucose or galactose,

- glucose oxidase and D-glucose,

- glycerin oxidase and glycerin,

- pyruvate oxidase and acid pyruvic or its salts,

- alcohol oxidase and alcohol (MeOH, EtOH),

- lactate oxidase and lactic acid and its salts,

- tyrosinase oxidase and tyrosine,

- uricase and uric acid or its salts,

- choline oxidase and choline,

- amino acid oxidase and amino acids.

Properly, the preparation of the mixture is mixed oxidizing agent immediately before hair coloring with the preparation from the primary products of the oxidation dyes In this regard, the dye preparation for Ready-to-use hair formed in this way must present preferably a pH value in the range of from 6 to 10. Especially preferred is the application of hair dye in a weak alkaline medium. Application temperatures may be in the range between 15 and 40 ° C. After a time of action of approximately 30 minutes, hair dye is removed by rinsing the hair to be dyed. Washing is avoided secondary hair when using a holder that contains strong surfactants, for example, coloring shampoo.

The following examples should clarify in one the object of the invention in more detail.

Examples

A base cream of the following was produced composition:

Hydrenol®D1 17.00 g Lorol®tec. 2 4.00 g Eumulgin®B23 1.50 g Texapon®NSO 4 40.00 g Dehyton®K5 25.00 g Water 12.50 g 1 Fatty alcohol C_ {16} -C_ {18} (INCI designation: Cetearyl alcohol) (Cognis) 2 fatty alcohol C_ {12} -C_ {18} (INCI designation: Coconut alcohol) (Cognis)  \ begin {minipage} [t] {155mm} ^ {3} Alcohol cetearylstearyl with about 20 units of oxide ethylene (INCI designation: Ceteareth-20) (Cognis) \ end {minipage}  \ begin {minipage} [t] {155mm} ^ {4} Sulfate lauryl ether, sodium salt (approximately 27.5% active substance; INCI designation: Sodium Laureth Sulfate) (Cognis) \ end {minipage}  \ begin {minipage} [t] {155mm} ^ {5} N, N-dimethyl-N- (amidopropyl C_ {8} -C_ {18} of coconut) ammonium-acetobetaine (approximately 30% of active substance; INCI designation: Aqua (water), Cocamidopropyl Betaine) (Cognis) \ end {minipage}

The substances Hydrenol®D, Lorol® and Eumulgin®B2 melted at 80 ° C, mixed with hot water at 80 ° C which it contained Texapon®NSO and Dehyton®K, and they were emulsified with stirring strong. Then the emulsion was cooled with weak agitation.

Coloring creams of the following composition:

Base cream 50.0 g Development component (E1-E10) 7.5 mmol Coupling component (K1-K11) 7.5 mmol Na 2 SO 3 (inhibitor) 1.0 g (NH 4) 2 SO 4 1.0 g 25% aqueous NH3 solution until pH = 10 Water up to 100 g

The components were mixed in order one after other. After adding the primary products of the dyes of oxidation and of the inhibitor the pH value of the emulsion was adjusted to 10 with concentrated ammonia solution, then filled with water up to 100g

The oxidative development of the coloration was carried carried out with a solution of hydrogen peroxide at 3% by weight as oxidation solution To do this, 100 g of emulsion were added to 50 g of hydrogen peroxide solution (3%) and mixed.

Coloring creams were applied on tufts of approximately 5 cm long human hair pattern, with 90% gray hair, but not specially treated previously and They left there for 30 minutes. After finishing the process of coloring, rinsed hair, washed with a regular shampoo and then then dried. To get the final color you they used the following coupling compounds and developing:

K1: 2-methyl-5-aminophenol K2: resorcinol K3: 2-Chloro-6-methyl-3-aminophenol K4: 2-methyl-4-chloro-5-aminophenol K5: 3-amino-6-methoxy-2-methylaminopyridine K6: m-aminophenol K7: 2,4-diaminophenoxyethanol K8: 1-naphthol K9: 1,3-bis- (2 ', 4'-diaminophenoxy) -propane K10: 2-methyl-5- (2'-hydroxyethyl) -aminophenol K11: 3,4-methylenedioxyaniline

The development agents used the following compounds:

E1: (according to invention) N, N'-bis- (2-hydroxy-5-aminobenzyl) -piperazine 4HCl (formula I: R 1, R 2, R 3 and R 4 = H, R 5 = formula II) E2: sulfate p-toluylenediamine E3: p-aminophenol E4: sulfate from 2,4,5,6-tetraaminopyrimidine E5: 3-methyl-4-aminophenol E6: 4-amino-2-aminomethyl-phenol \ cdot 2HCl E7: bis- (2-hydroxy-5-aminophenyl) -methane \ cdot 2HCl E8: 1,3-N, N'-bis- (2'-hydroxyethyl) -N, N'-bis- (4-aminophenyl) -diaminopropan-2-ol \ cdot 4HCl E9: 4,5-diamino-1- (2'-hydroxyethyl) -pyrazole 2H_ {2} SO_ {4} E10: sulfate 4-hydroxy-2,5,6-triaminopyrimidine

The results of the coloring are deduced from the following table:

In the examples with combinations of agents of development or coupling were used of each of the agents of development or coupling 3.75 mmol, so that the amount Total development agent or coupling agent was 7.5 mmol / 100 g of coloring cream.

19

Claims (10)

1. Use of derivatives of para-aminophenol of formula I, twenty in which R 1, R 2, R 3 and R 5, independently of each other, represent hydrogen, a C 1 -C 4 alkyl group, a group C 2 -C 4 hydroxyalkyl, R 2 and R 3 they also represent fluorine, chlorine, bromine, an alkoxy group C 1 -C 4 or a hydroxyalkoxy group C 2 -C 4, R 5 is also an acyl moiety with 1-8 C atoms or a group of formula II, twenty-one and R 4 represents a represents a hydrogen atom, an alkyl group, a hydroxyalkyl group C 2 -C 4, fluorine, chlorine, bromine and a group alkoxy C_ {1} -C_ {{}}, and its water soluble salts as a component of development for the production of oxidation colorations. 2. Use according to claim 1, characterized in that R5 is a group of formula II. 3. Use according to one of claims 1 or 2, characterized in that R5 of formula II is selected such that the 2-hydroxy-5-aminobenzyl substituents attached to the piperazinyl bridges are the same. Use according to one of claims 1 to 3, characterized in that R 4 and at least one of the substituents R 2 or R 3 is a hydrogen atom. 5. Use according to one of claims 1 to 4, characterized in that the compound according to formula I is N, N'-bis- (2-hydroxy-5-aminobenzyl) -piperazine • 4HCl. 6. Oxidation dyes for keratin fibers, especially for hair, characterized in that they contain in an aqueous support at least one para-aminophenol derivative of formula I, as well as at least one other development agent and / or coupling agent. 7. Oxidation dyes according to claim 6, characterized in that as a coupling component they contain at least one m-aminophenol, a naphthol, a resorcinol or a derivative of these compounds. 8. Oxidation dyes according to one of claims 6 or 7, characterized in that the aqueous support is an aqueous solution, a cream (emulsion), a gel or a foamy preparation. 9. Oxidation dyes according to one of claims 6 to 8, characterized in that they contain at least one direct dye for further modification of the color shades. Method for dyeing keratin fibers, especially human hair, characterized in that an oxidation dye according to one of claims 6 to 9 is mixed with a preparation of an oxidizing agent, is applied to the fibers at a temperature below 40 ° C and Wash again after an action time of at least 30 minutes.